Methyl α-phenylbutenoates

ABSTRACT

Methyl α-phenylbutenoates of the formula I ##STR1## where -- is a single or double bond and the index and the substituents have the following meanings: 
     n is 0, 1, 2, 3 or 4; 
     R 1  is nitro, cyano, halogen, alkyl, haloalkyl or alkoxy; 
     R 2  is hydrogen, nitro, cyano, halogen, alkyl, haloalkyl, alkoxy, alkylthio or alkoxycarbonyl; 
     R 3  is unsubst. or subst. alkyl, alkenyl or alkynyl; 
     an unsubst. or subst. saturated or mono-or diunsaturated ring which, in addition to carbon atoms, can contain one to three of the following heteroatoms as ring members: oxygen, sulfur and nitrogen, or 
     an unsubst. or subst. mono- or binuclear aromatic radical which, in addition to carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and an oxygen or sulfur atom or an oxygen or sulfur atom as ring members, 
     processes for their preparation and their use are described.

This application is a 371 of PCT/EP95/01554 filed Apr. 25, 1995.

The present invention relates to methyl α-phenylbutenoates of theformula I ##STR2## where ---- is a single or double bond and the indexand the substituents have the following meanings:

n is 0, 1, 2, 3 or 4, it being possible for the substituents R¹ to bedifferent if n is greater than 1;

R¹ is nitro, cyano, halogen, C_(1-C) ₄ -alkyl, C₁ -C₄ -haloalkyl or C₁-C₄ -alkoxy;

R² is hydrogen, nitro, cyano, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl,C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₄ -alkoxycarbonyl;

R³ is unsubst. or subst. alkyl, alkenyl or alkynyl;

an unsubst. or subst. saturated or mono-or diunsaturated ring which, inaddition to carbon atoms, can contain one to three of the followingheteroatoms as ring members: oxygen, sulfur and nitrogen, or

an unsubst. or subst. mono-or binuclear aromatic radical which, inaddition to carbon atoms, can contain one to four nitrogen atoms or oneor two nitrogen atoms and an oxygen or sulfur atom or an oxygen orsulfur atom as ring members.

The invention additionally relates to processes for preparing thesecompounds, mixtures containing them and their use for controllingharmful fungi or animal pests.

EP-A 513 580 discloses methyl α-phenylbutenoates with action againstharmful fungi or animal pests, which carry a 4-pyrazolyl-oxymethyleneradical in the ortho position. The action of these compounds isunsatisfactory, however, at low application rates.

It is an object of the present invention to provide compounds havingimproved actions.

We have found that this is achieved by the compounds I defined at theoutset. In addition, we have found processes for their preparation,mixtures containing them and methods for controlling harmful fungi andanimal pests using the compounds I.

The compounds I can be obtained by various methods known per se from theliterature.

For example, the compounds I are obtained by reaction of the benzylderivative of the formula II with a 3-hydroxy(dihydro)-pyrazole of theformula III in the presence of a base. ##STR3##

L in the formula II is a nucleophilically replaceable group, for examplehalogen, eg. chlorine, bromine or iodine, or an alkyl- or arylsulfonate,eg. methylsulfonate, trifluoromethylsulfonate, phenylsulfonate or4-methylphenylsulfonate.

The reaction is customarily carried out at from 0° C. to 80° C.,preferably from 20° C. to 60° C.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- andp-xylene, halogenated hydrocarbons such as methylene chloride,chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyiether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,nitriles such as acetonitrile and propionitrile, alcohols such asmethanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol,ketones such as acetone and methyl ethyl ketone, and also dimethylsulfoxide, dimethylformamide, dimethylacetamide,1,3-dimethylimidazolidin-2-one and1,2-dimethyltetrahydro-2(1H)-pyrimidine, preferably methylene chloride,acetone and dimethylformamide. Mixtures of the solvents mentioned canalso be used.

Suitable bases are generally inorganic compounds such as alkali metaland alkaline earth metal hydroxides (eg. lithium hydroxide, sodiumhydroxide, potassium hydroxide and calcium hydroxide), alkali metal andalkaline earth metal oxides (eg. lithium oxide, sodium oxide, calciumoxide and magnesium oxide), alkali metal and alkaline earth metalhydrides (eg. lithium hydride, sodium hydride, potassium hydride andcalcium hydride), alkali metal amides (eg. lithium amide, sodium amideand potassium amide), alkali metal and alkaline earth metal carbonates(eg. lithium carbonate and calcium carbonate) and also alkali metalhydrogen carbonates (eg. sodium hydrogen carbonate), organometalliccompounds, in particular alkali metal alkyls (eg. such as methyllithium,butyllithium and phenyllithium), alkylmagnesium halides (eg.methylmagnesiumchloride) and also alkali metal and alkaline earth metalalkoxides (eg. sodium methoxide, sodium ethoxide, potassium ethoxide,potassium tert-butoxide and dimethoxymagnesium), additionally organicbases, eg. tertiary amines such as trimethylamine, triethylamine,triisopropylethylamine and N-methylpiperidine, pyridine, substitutedpyridines such as collidine, lutidine and 4-dimethylaminopyridine andalso bicyclic amines.

Sodium hydroxide, potassium carbonate and potassium tert-butoxide areparticularly preferred.

The bases are in general used in equimolar amounts, in an excess or, ifappropriate, as a solvent.

It may be advantageous for the reaction to add a catalytic amount of acrown ether (eg. 18-crown-6 or 15-crown-5).

The reaction can also be carried out in two-phase systems consisting ofa solution of alkali metal or alkaline earth metal hydroxides orcarbonates in water and an organic phase (eg. aromatic and/orhalogenated hydrocarbons). Suitable phase-transfer catalysts in thiscase are, for example, ammonium halides and tetrafluoroborates (eg.benzyltriethylammonium chloride, benzyltributylammonium bromide,tetrabutylammonium chloride, hexadecyltrimethylammoniumbromide ortetrabutylammonium tetrafluoroborate) and also phosphonium halides (eg.tetrabutylphosphonium chloride and tetraphenylphosphonium bromide).

It may be advantageous for the reaction first to convert the3-hydroxy(dihydro)pyrazole with the base to the correspondinghydroxylate, which is then reacted with the benzyl derivative.

The starting substances II required for the preparation of the compoundsI are disclosed in EP-A 513 580. Compounds II in which L is chlorine orbromine are accordingly obtained by reaction of appropriate ethers(alkyl or aryl ethers) with halogenating agents Hal! (eg. borontrichloride, hydrogen bromide) in an inert solvent (eg. halogenstedand/or aromatic hydrocarbons) at from -30° C. to 40° C. ##STR4##

3-Hydroxypyrazoles IIIa and 3-hydroxydihydropyrazoles IIIb (or theirtautomeric form: 3-pyrazolones) are known from the literature or can beprepared by the methods described there IIIa: J. Heterocycl. Chem. 30(1993), 49; Chem. Ber. 107 (1974), 1318; Chem. Pharm. Bull. 19 (1971),1389; Tetrahedron Lett. 11 (1970), 875; Chem. Heterocycl. Comp. 5(1969), 527; Chem. Ber. 102 (1969), 3260; Chem. Ber. 109 (1976), 261; J.Org. Chem. 31 (1966), 1538; Tetrahedron 43 (1987), 607; IIIb: J. Med.Chem. 19 (1976), 715!.

The compounds I are obtained in a similar manner to the methodsdescribed in EP-A 513 580 by the processes compiled in the followingreaction scheme (with respect to the process parameters reference may bemade to the details in EP-A 513 580, whose disclosure is hereby includedwith respect to the preparation process). ##STR5##

With respect to the butenoic acid double bond, the compounds I can existboth as E- and Z-isomers. Both isomers can be used separately ortogether in the manner according to the invention. Mixtures of theisomers are preferred, in particular the E isomer (configuration withrespect to the carboxylate methyl position).

In the definitions of the symbols given in the above formulae,collective terms were used which are generally representative of thefollowing substituents:

halogen: fluorine, chlorine, bromine and iodine;

alkyl: saturated, straight-chain or branched hydrocarbon radicals having1 to 4 carbon atoms, eg. methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), it being possible for the hydrogen atomsthese in sic! groups to be partly or completely replaced by halogenatoms as mentioned above, eg. C₁ -C₂ -haloalkyl such as chloromethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl and pentafluoroethyl;

alkoxy: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), which are bonded to the structure via anoxygen atom (--O--);

alkoxycarbonyl: straight-chain or branched alkoxy groups having 1 to 4carbon atoms (as mentioned above), which are bonded to the structure viaa carbonyl group (--CO--);

alkylthio: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), which are bonded to the structure via asulfur atom (--S--);

unsubst. or subst. alkyl: saturated, straight-chain or branchedhydrocarbon radicals, in particular having 1 to 10 carbon atoms, eg. C₁-C₆ -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-di-methylbutyl, 2,3-dimethylbutyl, 3,3-dimethytbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

unsubst. or subst. alkenyl: unsaturated, straight-chain or branchedhydrocarbon radicals, in particular having 2 to 10 carbon atoms and adouble bond in any desired position, eg. C_(2-C) ₆ -alkenyl such asethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

alkynyl: straight-chain or branched hydrocarbon groups, in particularhaving 2 to 20 carbon atoms and a triple bond in any desired position,eg. C₂ -C₆ -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl,2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl,1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl,4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and1-ethyl-1-methyl-2-propynyl;

an unsubst. or subst. saturated or mono-or diunsaturated ring which, inaddition to carbon atoms, can contain one to three of the followingheteroatoms as ring members: oxygen, sulfur and nitrogen, for examplecarbocycles such as cyclopropyl, cyclopentyl, cyclohexyl,cyclopent-2-enyl, cyclohex-2-enyl, 5- to 6-membered, saturated orunsaturated heterocycles, containing one to three nitrogen atoms and/oran oxygen or sulfur atom, such as 2-tetrahydrofuranyl,3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidinyl, 2,3-dihydrofur-2-yl,2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl,2,4-dihydrothien-3-yl, 2,3-pyrrolin-2-yl, 2,3-pyrrolin-3-yl,2,4-pyrrolin-2-yl, 2,4-pyrrolin-3-yl, 2,3-isoxazolin-3-yl,3,4-isoxazolin-3-yl, 4,5-isoxazolin-3-yl, 2,3-isoxazolin-4-yl,3,4-isoxazolin-4-yl, 4,5-isoxazolin-4-yl, 2,3-isoxazolin-5-yl,3,4-isoxazolin-5-yl, 4,5-isoxazolin-5-yl, 2,3-isothiazolin-3-yl,3,4-isothiazolin-3-yl, 4,5-isothiazolin-3-yl, 2,3-isothiazolin-4-yl,3,4-isothiazolin-4-yl, 4,5-isothiazolin-4-yl, 2,3-isothiazolin-5-yl,3,4-isothiazolin-5-yl, 4,5-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl,2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl,2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl,3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl,4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl,4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-tetrahydropyridazinyl,4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl,4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl,1,3,5-tetrahydrotriazin-2-yl and 1,2,4-tetrahydrotriazin-3-yl,preferably 2-tetrahydrofuranyl, 2-tetrahydrothienyl, 2-pyrrolidinyl,3-isoxazolidinyl, 3-isothiazolidinyl, 1,3,4-oxazolidin-2-yl,2,3-dihydrothien-2-yl, 4,5-isoxazolin-3-yl, 3-piperidinyl,1,3-dioxan-5-yl, 4-piperidinyl, 2-tetrahydropyranyl,4-tetrahydropyranyl;

or an unsubst. or subst. mono-or binuclear aromatic ring system which,in addition to carbon atoms, can contain one to four nitrogen atoms orone or two nitrogen atoms and an oxygen or sulfur atom or an oxygen orsulfur atom as ring members, ie. aryl radicals such as phenyl andnaphthyl, preferably phenyl or 1- or 2-naphthyl, and hetaryl radicals,for example 5-membered ring heteroaromatics containing one to threenitrogen atoms and/or an oxygen or sulfur atom, such as 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl,5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,2,5-triazol-3-yl, 1,2,3-triazol-4-yl,1,2,3-triazol-5-yl, 1,2,3-triazol-4-yl, 5-tetrazolyl,1,2,3,4-thiatriazol-5-yl and 1,2,3,4-oxatriazol-5-yl, in particular3-isoxazolyl, 5-isoxazolyl, 4-oxazolyl, 4-thiazolyl,1,3,4-oxadiazol-2-yl and 1,3,4-thiadiazol-2-yl or, for example,6-membered ring heteroaromatics containing one to four nitrogen atoms asheteroatoms, such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and1,2,4,5-tetrazin-3-yl, in particular 2-pyridinyl, 3-pyridinyl,4-pyridinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl and4-pyridazinyl.

The addition of unsubst. or subst. with respect to alkyl, alkenyl andalkynyl groups is intended to express that these groups can be partly orcompletely halogenated (ie. the hydrogen atoms of these groups can cansic! be partly or completely replaced by identical or different halogenatoms such as mentioned above, preferably fluorine, chlorine andbromine, in particular fluorine and chlorine) and/or can carry one tothree, in particular one, of the following radicals:

cyano, nitro, C₁ -C₄ -alkoxy, C₁ -C₄ -halalkoxy sic!, C₁ -C₄ -alkylthioor an unsubst. or subst. mono-or binuclear aromatic ring system which,in addition to carbon atoms, can contain one to four nitrogen atoms orone or two nitrogen atoms and an oxygen or sulfur atom or an oxygen orsulfur atom as ring members, ie. aryl radicals such as phenyl andnaphthyl, preferably phenyl or 1- or 2-naphthyl, and hetaryl radicals,for example 5-membered ring heteroaromatics containing one to threenitrogen atoms and/or an oxygen or sulfur atom, such as 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl,5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,2,5-triazol-3-yl, 1,2,3-triazol-4-yl,1,2,3-triazol-5-yl, 1,2,3-triazol-4-yl, 5-tetrazolyl,1,2,3,4-thiatriazol-5-yl and 1,2,3,4-oxatriazol-5-yl, in particular3-isoxazolyl, 5-isoxazolyl, 4-oxazolyl, 4-thiazolyl,1,3,4-oxadiazol-2-yl and 1,3,4-thiadiazol-2-yl or, for example,6-membered ring heteroaromatics containing one to four nitrogen atoms asheteroatoms, such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and1,2,4,5-tetrazin-3-yl, in particular 2-pyridinyl, 3-pyridinyl,4-pyridinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl and4-pyridazinyl.

The addition of unsubst. or subst. with respect to the cyclic(saturated, unsaturated or aromatic) groups is intended to express thatthese groups can be partly or completely halogenated (ie. the hydrogenatoms of these groups can can sic! be partly or completely replaced byidentical or different halogen atoms such as mentioned above, preferablyfluorine, chlorine and bromine, in particular fluorine and chlorine)and/or can carry one to three of the following radicals: nitro, cyano,C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

The mono-or binuclear aromatic or heteroaromatic systems mentioned underthe radicals can in turn be partly or completely halogenated, ie. thehydrogen atoms of these groups can be partly or completely replaced byhalogen atoms such as fluorine, chlorine, bromine and iodine, preferablyfluorine and chlorine.

In addition to the halogen atoms designated, these mono-or binucleararomatic or heteroaromatic systems can additionally carry one to threeof the following substituents:

nitro;

cyano, thiocyanato;

alkyl, particularly C₁ -C₆ -alkyl as mentioned above, preferably methyl,ethyl, 1-methylethyl, 1,1-dimethylethyl, butyl, hexyl, in particularmethyl and 1-methylethyl;

C₁ -C₄ -haloalkyl, as mentioned above, preferably trichloromethyl,difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyland pentafluoroethyl;

C₁ -C₄ -alkoxy, preferably methoxy, ethoxy, 1-methylethoxy and1,1-dimethylethoxy, in particular methoxy;

C₁ -C₄ -haloalkoxy, particularly C₁ -C₂ -haloalkoxy, preferablydifluoromethoxy, triftuoromethoxy and 2,2,2-trifluoroethoxy, inparticular difluoromethoxy;

C₁ -C₄ -alkylthio, preferably methylthio and 1-methylethylthio, inparticular methylthio;

C₁ -C₄ -alkylamino such as methylamino, ethylamino, propylamino,1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylaminoand 1,1-dimethylethylamino, preferably methylamino and1,1-dimethylethylamino, in particular methylamino,

di-C₁ -C₄ -alkyiamino such as N,N-dimethylamino, N,N-diethylamino,N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino,N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino,N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino,N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino,N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino,N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino,N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino,N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino,N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino,N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino,N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino,N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino,N-(1-methylethyl)-N-(1-methylpropyl)amino,N-(1-methylethyl)-N-(2-methylpropyl)amino,N-(1,1-dimethylethyl)-N-(1-methylethyl)-amino,N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino,N-buty1-N-(1,1-dimethylethyl)amino,N-(1-methylpropyl)-N-(2-methylpropyl)amino,N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino andN-(1,1-dimethylethyl)-N-(2-methylpropyl)amino, preferablyN,N-dimethylamino and N,N-diethylamino, in particular N,N-dimethylamino;

C₁ -C₆ -alkylcarbonyl such as methylcarbonyl, ethylcarbonyl,propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl,1-methylpropylcarbonyl, 2-methylpropylcarbonyl,1,1-dimethylethylcarbonyl, pentylcarbonyl, 1-methylbutylcarbonyl,2-methylbutylcarbonyl, 3-methylbutylcarbonyl,1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl,2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl,1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl,4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl,1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl,2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl,3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl,1,1,2-trimethylpropylcarbonyl, 1,2,2-trimethylpropylcarbonyl,1-ethyl-1-methylpropylcarbonyl and 1-ethyl-2-methylpropylcarbonyl,preferably methylcarbonyl, ethylcarbonyl and 1,1-dimethylcarbonyl, inparticular ethylcarbonyl;

C₁ -C₆ -alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl,1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl,1,1-dimethylethoxycarbonyl, pentoxycarbonyl, 1-methylbutoxycarbonyl,2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl,2,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, hexyloxycarbonyl,1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl,1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl,3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl,1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl,1,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl,2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl,1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl,1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl,1-ethyl-1-methylpropoxycarbonyl and 1-ethyl-2-methylpropoxycarbonyl,preferably methoxycarbonyl, ethoxycarbonyl and1,1-dimethylethoxycarbonyl, in particular ethoxycarbonyl;

C₁ -C₆ -alkylaminocarbonyl such as methylaminocarbonyl,ethylaminocarbonyl, propylaminocarbonyl, 1-methylethylaminocarbonyl,butylaminocarbonyl, 1-methylpropylaminocarbonyl,2-methylpropylaminocarbonyl, 1,1-dimethylethylaminocarbonyl,pentylaminocarbonyl, 1-methylbutylaminocarbonyl,2-methylbutylaminocarbonyl, 3-methylbutylaminocarbonyl,2,2-dimethylpropylaminocarbonyl, 1-ethylpropylaminocarbonyl,hexylaminocarbonyl, 1,1-dimethylpropylaminocarbonyl,1,2-dimethylpropylaminocarbonyl, 1-methylpentylaminocarbonyl,2-methylpentylaminocarbonyl, 3-methylpentylaminocarbonyl,4-methylpentylaminocarbonyl, 1,1-dimethylbutylaminocarbonyl,1,2-dimethylbutylaminocarbonyl, 1,3-dimethylbutylaminocarbonyl,2,2-dimethylbutylaminocarbonyl, 2,3-dimethylbutylaminocarbonyl,3,3-dimethylbutylaminocarbonyl, 1-ethylbutylaminocarbonyl,2-ethylbutylaminocarbonyl, 1,1,2-trimethylpropylaminocarbonyl,1,2,2-trimethylpropylaminocarbonyl, 1-ethyl-1-methylpropylaminocarbonyland 1-ethyl-2-methylpropylaminocarbonyl, preferably methylaminecarbonylsic! and ethylaminecarbonyl sic!, in particular methylaminocarbonyl;

di-C₁ -C₆ -alkylaminocarbonyl, particularly di-C₁ -C₄-alkylaminocarbonyl such as N,N-dimethylaminocarbonyl,N,N-diethylaminocarbonyl, N,N-dipropylaminocarbonyl,N,N-di(1-methylethyl)aminocarbonyl, N,N-dibutylaminocarbonyl,N,N-di(1-methylpropyl)aminocarbonyl,N,N-di(2-methylpropyl)aminocarbonyl,N,N-di(1,1-dimethylethyl)aminocarbonyl, N-ethyl-N-methylaminocarbonyl,N-methyl-N-propylaminocarbonyl, N-methyl-N-(1-methylethyl)aminocarbonyl,N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl,N-methyl-N-(2-methylpropyl)aminocarbonyl,N-(1,1-dimethylethyl)-N-methylaminocarbonyl,N-ethyl-N-propylaminocarbonyl, N-ethyl-N-(1-methylethyl)aminocarbonyl,N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl,N-ethyl-N-(2-methylpropyl)aminocarbonyl,N-ethyl-N-(1,1-dimethylethyl)aminocarbonyl,N-(1-methylethyl)-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl,N-(1-methylpropyl)-N-propylaminocarbonyl,N-(2-methylpropyl)-N-propylaminocarbonyl,N-(1,1-dimethylethyl)-N-propylaminocarbonyl,N-butyl-N-(1-methylethyl)aminocarbonyl,N-(1-methylethyl)-N-(1-methylpropyl)aminocarbonyl,N-(1-methylethyl)-N-(2-methylpropyl)aminocarbonyl,N-(1,1-di-methylethyl)-N-(1-methylethyl)aminocarbonyl,N-butyl-N-(1-methylpropyl)aminocarbonyl,N-butyl-N-(2-methylpropyl)aminocarbonyl,N-butyl-N-(1,1-dimethylethyl)aminocarbonyl,N-(1-methylpropyl)-N-(2-methyl-propyl)aminocarbonyl,N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminocarbonyl andN-(1,1-dimethylethyl)-N-(2-methylpropyl)aminocarbonyl, preferablyN,N-dimethylaminocarbonyl and N,N-diethylaminecarbonyl sic!, inparticular N,N-dimethylaminocarbonyl;

C₁ -C₆ -alkylcarboxyl such as methylcarboxyl, ethylcarboxyl,propylcarboxyl, 1-methylethylcarboxyl, butylcarboxyl,1-methylpropylcarboxyl, 2-methylpropylcarboxyl,1,1-dimethylethylcarboxyl, pentylcarboxyl, 1-methylbutylcarboxyl,2-methylbutylcarboxyl, 3-methylbutylcarboxyl,1,1-dimethylpropylcarboxyl, 1,2-dimethylpropylcarboxyl,2,2-dimethylpropylcarboxyl, 1-ethylpropylcarboxyl, hexylcarboxyl,1-methylpentylcarboxyl, 2-methylpentylcarboxyl, 3-methylpentylcarboxyl,4-methylpentylcarboxyl, 1,1-dimethylbutylcarboxyl,1,2-dimethylbutylcarboxyl, 1,3-dimethylbutylcarboxyl,2,2-dimethylbutylcarboxyl, 2,3-dimethylbutylcarboxyl,3,3-dimethylbutylcarboxyl, 1-ethylbutylcarboxyl, 2-ethylbutylcarboxyl,1,1,2-trimethylpropylcarboxyl, 1,2,2-trimethylpropylcarboxyl,1-ethyl-1-methylpropylcarboxyl and 1-ethyl-2-methylpropylcarboxyl,preferably methylcarboxyl, ethylcarboxyl and 1,1-dimethylethylcarbonyl,in particular methylcarboxyl and 1,1-dimethylethylcarboxyl;

C₁ -C₆ -alkylcarbonylamino such as methylcarbonylamino,ethylcarbonylamino, propylcarbonylamino, 1-methylethylcarbonylamino,butylcarbonylamino, 1-methylpropylcarbonylamino,2-methylpropylcarbonylamino, 1,1-dimethylethylcarbonylamino,pentylcarbonylamino, 1-methylbutylcarbonylamino,2-methylbutylcarbonylamino, 3-methylbutylcarbonylamino,2,2-dimethylpropylcarbonylamino, 1-ethylpropylcarbonylamino,hexylcarbonylamino, 1,1-dimethylpropylcarbonylamino,1,2-dimethylpropylcarbonylamino, 1-methylpentylcarbonylamino,2-methylpentylcarbonylamino, 3-methylpentylcarbonylamino,4-methylpentylcarbonylamino, 1,1-dimethylbutylcarbonylamino,1,2-dimethylbutylcarbonylamino, 1,3-dimethylbutylcarbonylamino,2,2-dimethylbutylcarbonylamino, 2,3-dimethylbutylcarbonylamino,3,3-dimethylbutylcarbonylamino, 1-ethylbutylcarbonylamino,2-ethylbutylcarbonylamino, 1,1,2-trimethylpropylcarbonylamino,1,2,2-trimethylpropylcarbonylamino, 1-ethyl-1-methylpropylcarbonylaminoand 1-ethyl-2-methylpropylcarbonylamino, preferably methylcarbonylaminoand ethylcarbonylamino, in particular ethylcarbonylamino;

C₃ -C₇ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl, preferably cyclopropyl, cyclopentyl andcyclohexyl, in particular cyclopropyl;

C₃ -C₇ -cycloalkoxysuch as cyclopropoxy, cyclobutoxy, cyclopentoxy,cyclohexyloxy and cycloheptyloxy, preferably cyclopentoxy andcyclohexyloxy, in particular cyclohexyloxy;

C₃ -C₇ -cycloalkylthio such as cyclopropylthio, cyclobutylthio,cyclopentylthio, cyclohexylthio and cycloheptylthio, preferablycyclohexylthio;

C₃ -C₇ -cycloalkylamino such as cyclopropylamino, cyclobutylamino,cyclopentylamino, cyclohexylamino and cycloheptylamino, preferablycyclopropylamino and cyclohexylamino, in particular cyclopropylamino;

Two adjacent radicals on R³ can have the meaning of an oxy-C₁ -C₂-alkylidenoxy chain which is unsubstituted or substituted by fluorine,such as eg. --O--CH₂ --O, --O--CF₂ --O--, --O--CH₂ CH₂ --O-- or --O--CF₂CF₂ --O--, or a C₃ -C₄ -alkylidene chain, such as eg. propylidene orbutylidene.

With respect to their biological action, compounds I are preferred inwhich n is 0 or 1.

Equally, compounds I are preferred in which R¹ is halogen, C₁ -C₄-alkyl, C₁ -C₂ -haloalkyl or C₁ -C₂ -alkoxy.

Additionally, compounds I are preferred in which R² is hydrogen, nitro,halogen, C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl or C₁ -C₂ -alkoxycarbonyl.

In addition, compounds I are preferred in which R³ is unsubst. or subst.C₁ -C₄ -alkyl or C₃ -C₆ -cycloalkyl.

Equally, compounds I are preferred in which R³ is an unsubst. or subst.saturated or mono-or diunsaturated ring which, in addition to carbonatoms, can contain one to three of the following heteroatoms as ringmembers: oxygen, sulfur and nitrogen.

Additionally, compounds I are preferred in which R³ is an unsubst. orsubst. mono-or binuclear aromatic radical which, in addition to carbonatoms, can contain one to four nitrogen atoms or one or two nitrogenatoms and an oxygen or sulfur atom or an oxygen or sulfur atom as ringmembers.

In addition, compounds I are preferred in which R³ is an unsubst. orsubst. 5-membered ring heteroaromatic.

In addition, compounds I are preferred in which R³ is an unsubst. orsubst. 6-membered ring heteroaromatic.

In particular, compounds I are preferred in which R¹ is hydrogen (n=0),chlorine, methyl or trifluoromethyl.

In particular, compounds I are additionally preferred in which R² ishydrogen, halogen, methyl, trifluoromethyl or methoxycarbonyl.

Equally, compounds I are in particular preferred in which R³ is C₁ -C₄-alkyl.

Additionally, compounds I are in particular preferred in which R³ is C₃-C₆ -cycloalkyl which can carry one to three C₁ -C₄ -alkyl groups.

In particular, compounds I are in addition preferred in which R³ isunsubst. or subst. phenyl.

In particular, compounds I are also preferred in which R³ is unsubst. orsubst. pyridyl or pyrimidyl.

In particular, those compounds I are preferred in which R³ isunsubstituted or substituted phenyl or benzyl. Suitable substituents ofthe phenyl radical in these cases are preferably halogen, cyano, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkyl, C₁ -C₂ -haloalkoxy, phenyland oxy-C₁ -C₂ -alkylidenoxy.

Also preferred are those compounds I in which R³ is unsubstituted orsubstituted five-membered ring heteroaromatics such as eg. thiazolyl,isoxazolyl or oxazolyl. Suitable substituents of the five-membered ringheteroaromatics are preferably halogen, cyano, C₁ -C₆ -alkyl, C₁ -C₆-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₂ -haloalkoxy and phenyl.

Also preferred are those compounds I in which R³ is unsubstituted orsubstituted six-membered ring heteroaromatics, such as eg. pyridyl,pyrimidyl, pyridazinyl or pyrazinyl. Suitable substituents of thesix-membered ring heteroaromatics are preferably halogen, cyano, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkyl, C₁ -C₂ -haloalkoxy andphenyl.

Examples of particularly preferred compounds I are compiled in thefollowing tables.

Table 1

Compounds of the general formula I.1 in which R² is hydrogen and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A. ##STR6##

Table 2

Compounds of the general formula I.2 in which R² is hydrogen and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A. ##STR7##

Table 3

Compounds of the general formula I.1 in which R² is 4-Cl and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A.

Table 4

Compounds of the general formula I.1 in which R² is 4-Br and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A.

Table 5

Compounds of the general formula I.1, in which R² is 5-CH₃ and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A.

Table 6

Compounds of the general formula I.1, in which R² is 5-CF₃ and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A.

Table 7

Compounds of the general formula I.1, in which R² is 4-CO₂ CH₃ and thecombination of the substituents R_(n) ¹ and R³ for one compound in eachcase corresponds to one line of Table A.

                  TABLE A                                                         ______________________________________                                        R.sup.1.sub.n    R.sup.3                                                      ______________________________________                                        H                C.sub.6 H.sub.5                                              3-Cl             C.sub.6 H.sub.5                                              4-Cl             C.sub.6 H.sub.5                                              6-Cl             C.sub.6 H.sub.5                                              4-F              C.sub.6 H.sub.5                                              4-OCH.sub.3      C.sub.6 H.sub.5                                              3-CH.sub.3       C.sub.6 H.sub.5                                              6-CH.sub.3       C.sub.6 H.sub.5                                              H                2-F--C.sub.6 H.sub.4                                         H                3-F--C.sub.6 H.sub.4                                         H                4-F--C.sub.6 H.sub.4                                         H                2,3-F.sub.2 --C.sub.6 H.sub.3                                H                2,4-F.sub.2 --C.sub.6 H.sub.3                                H                2,5-F.sub.2 --C.sub.6 H.sub.3                                H                2,6-F.sub.2 --C.sub.6 H.sub.3                                H                3,4-F.sub.2 --C.sub.6 H.sub.3                                H                3,5-F.sub.2 --C.sub.6 H.sub.3                                H                2-Cl--C.sub.6 H.sub.4                                        H                3-Cl--C.sub.6 H.sub.4                                        H                4-Cl--C.sub.6 H.sub.4                                        3-Cl             4-Cl--C.sub.6 H.sub.4                                        4-Cl             4-Cl--C.sub.6 H.sub.4                                        6-Cl             4-Cl--C.sub.6 H.sub.4                                        4-F              4-Cl--C.sub.6 H.sub.4                                        4-OCH.sub.3      4-Cl--C.sub.6 H.sub.4                                        3-CH.sub.3       4-Cl--C.sub.6 H.sub.4                                        6-CH.sub.3       4-Cl--C.sub.6 H.sub.4                                        H                2,3-Cl.sub.2 --C.sub.6 H.sub.3                               H                2,4-Cl.sub.2 --C.sub.6 H.sub.3                               H                2,5-Cl.sub.2 --C.sub.6 H.sub.3                               H                2,6-Cl.sub.2 --C.sub.6 H.sub.3                               H                3,4-Cl.sub.2 --C.sub.6 H.sub.3                               H                3,5-Cl.sub.2 --C.sub.6 H.sub.3                               H                2,3,4-Cl.sub.3 --C.sub.6 H.sub.2                             H                2,3,5-Cl.sub.3 --C.sub.6 H.sub.2                             H                2,3,6-Cl.sub.3 --C.sub.6 H.sub.2                             H                2,4,5-Cl.sub.3 --C.sub.6 H.sub.2                             H                2,4,6-Cl.sub.3 --C.sub.6 H.sub.2                             H                3,4,5-Cl.sub.3 --C.sub.6 H.sub.2                             H                2-Br--C.sub.6 H.sub.4                                        H                3-Br--C.sub.6 H.sub.4                                        H                4-Br--C.sub.6 H.sub.4                                        H                2,4-Br.sub.2 --C.sub.6 H.sub.3                               H                2-Br, 4-F--C.sub.6 H.sub.3                                   H                2-Br, 4-Cl--C.sub.6 H.sub.3                                  H                2-F, 4-Cl--C.sub.6 H.sub.3                                   H                3-F, 4-Cl--C.sub.6 H.sub.3                                   H                3-Cl, 5-F--C.sub.6 H.sub.3                                   H                2-Cl, 4-F--C.sub.6 H.sub.3                                   H                2-CN--C.sub.6 H.sub.4                                        H                3-CN--C.sub.6 H.sub.4                                        H                4-CN--C.sub.6 H.sub.4                                        H                3-CN, 4-Cl--C.sub.6 H.sub.3                                  H                4-NO.sub.2 --C.sub.6 H.sub.4                                 H                2-CH.sub.3 --C.sub.6 H.sub.4                                 H                3-CH.sub.3 --C.sub.6 H.sub.4                                 H                4-CH.sub.3 --C.sub.6 H.sub.4                                 H                2,4-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                2,5-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                2,5-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                2,6-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                3,4-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                3,5-(CH.sub.3).sub.2 --C.sub.6 H.sub.3                       H                2,4,6-(CH.sub.3).sub.3 --C.sub.6 H.sub.2                     H                3,4,5-(CH.sub.3).sub.3 --C.sub.6 H.sub.2                     H                2-CH.sub.3, 4-Cl--C.sub.6 H.sub.3                            H                2-Cl, 4-CH.sub.3 --C.sub.6 H.sub.3                           H                3-CH.sub.3, 4-Cl--C.sub.6 H.sub.3                            H                3-Cl, 5-CH.sub.3 --C.sub.6 H.sub.3                           H                2-CN, 4-CH.sub.3 --C.sub.6 H.sub.3                           H                2-CH.sub.3, 4-CN--C.sub.6 H.sub.3                            H                4-(C.sub.2 H.sub.5)--C.sub.6 H.sub.4                         H                4- C(CH.sub.3).sub.3 !--C.sub.6 H.sub.4                      H                3-(C.sub.6 H.sub.5)--C.sub.6 H.sub.4                         H                4-(C.sub.6 H.sub.5)--C.sub.6 H.sub.4                         H                2-CF.sub.3 --C.sub.6 H.sub.4                                 H                3-CF.sub.3 --C.sub.6 H.sub.4                                 H                4-CF.sub.3 --C.sub.6 H.sub.4                                 H                3,5-(CF.sub.3).sub.2 --C.sub.6 H.sub.3                       H                2-Cl, 4-CF.sub.3 --C.sub.6 H.sub.3                           H                2-OCH.sub.3 --C.sub.6 H.sub.4                                H                3-OCH.sub.3 --C.sub.6 H.sub.4                                H                4-OCH.sub.3 --C.sub.6 H.sub.4                                H                2,4-(OCH.sub.3).sub.2 --C.sub.6 H.sub.3                      H                3,4-(OCH.sub.3).sub.2 --C.sub.6 H.sub.3                      H                2,5-(OCH.sub.3).sub.2 --C.sub.6 H.sub.3                      H                3,5-(OCH.sub.3).sub.2 --C.sub.6 H.sub.3                      H                3,4,5-(OCH.sub.3).sub.3 --C.sub.6 H.sub.2                    H                2-CH.sub.3, 4-OCH.sub.3 --C.sub.6 H.sub.3                    H                2-Cl, 4-OCH.sub.3 --C.sub.6 H.sub.3                          H                4-OCF.sub.3 --C.sub.6 H.sub.4                                H                2-OCHF.sub.2 --C.sub.6 H.sub.4                               H                3-OCHF.sub.2 --C.sub.6 H.sub.4                               H                4-OCHF.sub.2 --C.sub.6 H.sub.4                               H                4-(OCF.sub.2 CHF.sub.2)--C.sub.6 H.sub.4                     H                2-F, 4-OCHF.sub.2 --C.sub.6 H.sub.3                          H                4-(OCH.sub.2 CH.sub.3)--C.sub.6 H.sub.4                      H                4- OC(CH.sub.3).sub.3 !--C.sub.6 H.sub.4                     H                3-(CO.sub.2 CH.sub.3)--C.sub.6 H.sub.4                       H                4-(CO.sub.2 CH.sub.3)--C.sub.6 H.sub.4                       H                4- CO.sub.2 C(CH.sub.3).sub.3 !--C.sub.6 H.sub.4             H                2,3- O--CH.sub.2 --O!--C.sub.6 H.sub.3                       H                3,4- O--CH.sub.2 --O!--C.sub.6 H.sub.3                       H                3,4- O--C(CH.sub.3).sub.2 --O!--C.sub.6 H.sub.3              H                3,4- O--CH.sub.2 CH.sub.2 --O!--C.sub.6 H.sub.3              H                2,3- (CH.sub.2).sub.4 !--C.sub.6 H.sub.3                     H                3,4- (CH.sub.2).sub.4 !--C.sub.6 H.sub.3                     H                CH.sub.3                                                     H                CH.sub.2 CH.sub.3                                            H                CH.sub.2 CH.sub.2 CH.sub.3                                   H                C(CH.sub.3).sub.2                                            H                CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                          H                CHCH(CH.sub.3).sub.2                                         H                CH(CH.sub.3)CH.sub.2 CH.sub.3                                H                C(CH.sub.3).sub.3                                            H                Cyclopropyl                                                  H                Cyclohexyl                                                   H                Pyridin-2-yl                                                 H                5-CF.sub.3 -pyridin-2-yl                                     H                3,4- OCF.sub.2 O!--C.sub.6 H.sub.3                           H                CH.sub.2 --C.sub.6 H.sub.5                                   H                Pyrazin-2-yl                                                 H                5-Chloropyridin-2-yl                                         ______________________________________                                    

The methyl α-phenylbutenoates of the formula I according to theinvention are suitable for controlling harmful fungi and animal pests ofthe insects, arachnids and nematodes class. They can be employed asfungicides and pesticides in crop protection and in the hygiene, storedmaterial protection and veterinary sectors.

The harmful insects include:

from the order of the butterflies (Lepidoptera), for example, Adoxophyesorana, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Cacoecia murinana,Capua reticulana, Choristoneura fumiferana, Chilo partellus,Choristoneura occidentalis, Cirphis unipuncta, Cnaphalocrocis medinails,Crocidolomia binotalis, Cydia pomonella, Dendrolimus pini, Diaphanianitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpuslignosellus, Eupoecilia ambiguella, Feltia subterranea, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera scitella, Lithocolletis blancardella,Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantriamonacha, Lyonetia clerkella, Manduca sexta, Malacosoma neustria,Mamestra brassicae, Mocis repanda, Operophthera brumata, Orgyiapseudotsugata, Ostrinia nubilalis, Pandemis heparana, Panolis flammea,Pectinophora gossypiella, Phthorimaea operculella, Phyllocnistiscitrella, Pieris brassicae, Plathypena scabra, Platynota stultana,Plutella xylostella, Prays citri, Prays oleae, Prodenia sunia, Prodeniaornithogalli, Pseudoplusia includens, Rhyacionia frustrana,Scrobipalpula absoluta, Sesamia inferens, Sparganothis pilleriana,Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura,Syllepta derogata, Synanthedon myopaeformis, Thaumatopoea pityocampa,Tortrix viridana, Trichoplusia ni, Tryporyza incertulas, Zeirapheracanadensis, further Galleria mellonella and Sitotroga cerealella,Ephestia cautella, Tineola bisselliella;

from the order of the beetles (Coleoptera), for example, Agrioteslineatus, Agriotes obscurus, Anthonomus grandis, Anthonomus pomorum,Apion vorax, Atomaria linearis, Blastophagus piniperda, Cassidanebulosa, Cerotoma trifurcata, Ceuthorhynchus assimilis, Ceuthorhynchusnapi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi,Dendroctonus refipennis, Diabrotica longicornis, Diabrotica 12-punctata,Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis,Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis,Hypera postica, Ips typographus, Lama bilineata, Lama melanopus,Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrusoryzophilus, Melanotus communis, Meligethes aeneus, Melolonthahippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchussulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phylloperthahorticola, Phyllophaga sp., Phyllotreta chrysocephala, Phyllotretanemorum, Phyllotreta striolata, Popillia japonica, Psylliodes napi,Scolytus intricatus, Sitona lineatus,

further Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Sitophilusgranaria, Lasioderma serricorne, Oryzaephilus surinamensis, Rhyzoperthadominica, Sitophilus oryzae, Tribolium castaneum, Trogoderma granarium,Zabrotes subfasciatus;

from the order of the dipterous insects (Diptera), for example,Anastrepha ludens, Ceratitis capitata, Contarinia sorghicola, Dacuscucurbitae, Dacus oleae, Dasineura brassicae, Delia coarctata, Deliaradicum, Hydrellia griseola, Hylemyia platura, Liriomyza sativae,Liriomyza trifolii, Mayetiola destructor, Orseolia oryzae, Oscinellafrit, Pegomya hyoscyami, Phorbia antiqua, Phorbia brassicae, Phorbiacoarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tipula oleracea,Tipula paludosa,

further Aedes aegypti, Aedes vexans, Anopheles maculipennis, Chrysomyabezziana, Chrysomya hominivorax, Chrysomya macellaria, Cordylobiaanthropophaga, Culex pipiens, Fannia canicularis, Gasterophilusintestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosisequestris, Hypoderma lineata, Lucilia caprina sic!, Lucilia cuprina,Lucilia sericata, Musca domestica, Muscina stabulans, Oestrus ovis,Tabanus bovinus, Simulium damnosum;

from the order of the thrips (Thysanoptera), for example, Franklinleilafusca, Frankliniella occidentalis, Frankliniella tritici, Haplothripstritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci;

from the order of the hymenopterous insects (Hymenoptera), for example,Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampaminuta, Hoplocampa testudinea, Iridomyrmes humilis, Iridomyrmexpurpureus, Monomorium pharaonis, Solenopsis geminata, Solenopsisinvicta, Solenopsis richteri;

from the order of the bed bugs (Heteroptera), for example, Acrosternumhilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus,Dysdercus intermedius, Eurygaster integriceps, Euschistusimpictiventris, Leptoglossus phyllopus, Lygus hesperus, Lyguslineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubeainsularis, Thyanta perditor;

from the order of the plant-sucking insects (Homoptera), for example,Acyrthosiphon onobrychis, Acyrthosiphon pisum, Adelges laricis,Aonidiella aurantii, Aphidula nasturtii, Aphis fabae, Aphis gossypii,Aphis pomi, Aulacorthum solani, Bemisia tabaci, Brachycaudus cardui,Brevicoryne brassicae, Dalbulus maidis, Dreyfusia nordmannianae,Dreyfusia piceae, Dysaphis radicola, Empoasca fabae, Eriosoma lanigerum,Laodelphax striatella, Macrosiphum avenae, Macrosiphum euphorbiae,Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzuspersicae, Myzus cerasi, Nephotettix cincticeps, Nilaparvata lugens,Perkinsleila saccharicida, Phorodon humuli, Planococcus citri, Psyllamall, Psylla piri, Psylla pyricol, Quadraspidiotus perniciosus,Rhopalosiphum maidis, Saissetia oleae, Schizaphis graminum, Selenaspidusarticulatus, Sitobion avenae, Sogatella furcifera, Toxoptera citricida,Trialeurodes abutilonea, Trialeurodes vaporariorum, Viteus vitifolii;

from the order of the termites (Isoptera), for example, Calotermesflavicollis, Leucotermes flavipes, Macrotermes subhyalinus, Odontotermesformosanus, Reticulitermes lucifugus, Termes natalensis;

from the order of the orthopterous insects (Orthoptera), for example,Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes,Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana,Schistocerca peregrina, Stauronotus maroccanus, Schistocerca gregaria,further Acheta domestica, Blatta orientalis, Blattella germanica,Periplaneta americana;

from the order of the Arachnoidea, for example, phytophagous mites suchas Aculops lycopersicae, Aculops pelekassi, Aculus schlechtendali,Brevipalpus phoenicis, Bryobia praetiosa, Eotetranychus carpini,Eutetranychus banksii, Eriophyes sheldoni, Oligonychus pratensis,Panonychus ulmi, Panonychus citri, Phyllocoptruta oleivora,Polyphagotarsonemus latus, Tarsonemus pallidus, Tetranychuscinnabarinus, Tetranychus kanzawai, Tetranchus pacificus, Tetranychusurticae, ticks such as Amblyomma americanum, Amblyomma variegatum, Argaspersicus, Boophilus annulatus, Boophilus decoloratus, Boophilusmicroplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus,Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Rhipicephalusappendiculatus and Rhipicephalus evertsi as well as animal-parasiticmites such as Dermanyssus gallinae, Psoroptes ovis and Sarcoptesscabiei;

from the class of the nematodes, for example, root gall nematodes, eg.Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica,cyst-forming nematodes, z.B. Globodera pallida, Globodera rostochiensis,Heterodera avenae, Heterodera glycines, Heterodera schachtii, migratoryendoparasites and semi-endoparasitic nematodes, eg. Heliocotylenchusmulticinctus, Hirschmanniella oryzae, Hoplolaimus spp, Pratylenchusbrachyurus, Pratylenchus fallax, Pratylenchus penetrans, Pratylenchusvulnus, Radopholus similis, Rotylenchus reniformis, Scutellonema bradys,Tylenchulus semipenetrans, stem and leaf eelworms eg. Anguina tritici,Aphelenchoides besseyi, Ditylenchus angustus, Ditylenchus dipsaci, virusvectors, eg. Longidorus spp, Trichodorus christei, Trichodorusviruliferus, Xiphinema index, Xiphinema mediterraneum.

The active compounds can be applied as such, in the form of theirformulations or the application forms prepared therefrom, eg. in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dust compositions,scattering compositions or granules, by spraying, atomizing, dusting,scattering or watering. The application forms depend entirely on theintended uses; in each case they should if possible guarantee the finestdispersion of the active compounds according to the invention.

The methyl α-phenylbutenoates of the formula I are in some casessystemically active as fungicides. They can be employed as foliar andsoil fungicides against a broad spectrum of phytopathogenic fungi, inparticular from the Ascomycetes, Deuteromycetes, Phycomycetes andBasidiomycetes classes.

They are of particular importance for the control of a multiplicity offungi on various crop plants such as wheat, rye, barley, oats, rice,corn, grass, cotton, soybeans, coffee, sugar cane, grapes, fruit anddecorative plants and vegetable plants such as cucumbers, beans andcucurbits, and on the seeds of these plants.

The compounds I are specifically suitable for the control of thefollowing plant diseases:

Erysiphe graminis (powdery mildew) in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Podosphaera leucotricha on apples,

Uncinula necator on vines,

Puceinia species on cereals,

Rhizoctonia species on cotton and grass,

Ustilago species on cereals and sugar cane,

Venturia inaequalis (scab) on apples,

Helminthosporium species on cereals,

Septoria nodorum on wheat,

Botrytis cinerea (gray mold) on strawberries, vines,

Cercospora arachidicola on groundnuts,

Pseudocercosporella herpotrichoides on wheat, barley,

Pyricularia oryzae on rice,

Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on various plants,

Plasmopara viticola on vines,

Alternaria species on vegetables and fruit.

The novel compounds can also be employed in the protection of materials(preservation of wood), eg. against Paecilomyces variotii.

They can be converted into the customary formulations, such assolutions, emulsions, suspensions, dusts, powders, pastes or granules.The use forms here depend on the particular intended use; in each casethey should if possible guarantee the finest dispersion of the activecompounds.

The formulations are prepared in a known manner, eg. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, where if water is used as a diluent otherorganic solvents can also be used as auxiliary solvents.

Suitable auxiliaries for this purpose are mainly:

solvents such as aromatics (eg. xylene), chlorinated aromatics (eg.chlorobenzenes), paraffins (eg. petroleum fractions), alcohols (eg.methanol, butanol), ketones (eg. cyclohexanone), amines (eg.ethanolamine, dimethylformamide) and water;

carriers such as ground natural minerals (eg. kaolins, aluminas, talc,chalk) and ground synthetic minerals (eg. highly disperse silica,silicates);

emulsifiers such as nonionic and anionic emulsifiers (eg.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and

dispersants such as lignin-sulfite waste liquors and methylcellulose.

Suitable surface-active substances are the alkali metal, alkaline earthmetal and ammonium salts of aromatic sulfonic acids, eg. lignosulfonic,phenolsulfonic, naphthalenesulfonic and dibutylnaphthalenesulfonic acid,and also of fatty acids, alkyl- and alkylarylsulfonates, alkyl-, laurylether and fatty alcohol sulfates, as well as salts of sulfated hexa-,hepta- and octadecanols, and also of fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and its derivatives withformaldehyde, condensation products of naphthalene or of thenaphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctyl-, octal- or nonylphenol,alkylphenol or tributylphenylpolyglycol ether, alkylaryl polyetheralcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenesic!, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignin-sulfite waste liquors or methylcellulose.

Aqueous use forms can be prepared from emulsion concentrates,dispersions, pastes, wettable powders or water-dispersible granules byaddition of water. To prepare emulsions, pastes or oil dispersions, thesubstrates sic! can be homogenized in water as such or dissolved in anoil or solvent, by means of wetting agents, adhesives, dispersants oremulsifiers. However, concentrates consisting of active substance,wetting agent, adhesive, dispersant or emulsifier and possibly solventor oil can also be prepared which are suitable for dilution with water.

Powder, scattering and dusting compositions can be prepared by mixing orjoint grinding of the active substances with a solid carrier.

Granules, eg. coated, impregnated and homogeneous granules, can beprepared by binding the active compounds to solid carriers.

Solid carriers are mineral earths such as silica gel, silicic acids,silica gels sic!, silicates, talc, kaolin, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesiumsulfate, magnesium oxide, ground synthetic materials, fertilizers, suchas ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas andvegetable products, such as cereal flour, tree bark meal, wood meal andnutshell meal, cellulose powder or other solid carriers. The activecompound concentrations in the ready-to-use preparations can be variedwithin relatively wide ranges.

Very generally, the compositions contain from 0.0001 to 95% by weight ofactive compound.

Formulations containing more than 95% by weight of active compound canbe applied highly successfully in the ultra-low volume process (ULV), iteven being possible to use the active compound without additives.

For use as fungicides, concentrations of from 0.01 to 95% by weight,preferably of from 0.5 to 90% by weight, of active compound arerecommended. For use as insecticides, formulations containing from0.0001 to 10% by weight, preferably from 0.01 to 1% by weight, of activecompound are suitable.

The active compounds are normally employed in a purity of from 90% to100%, preferably from 95% to 100% (according to NMR spectrum).

Examples of such preparations are:

I. a solution of 90 parts by weight of a compound I according to theinvention and 10 parts by weight of N-methyl-α-pyrrolidone, which issuitable for application in the form of very small drops;

II. a solution of 20 parts by weight of a compound I according to theinvention in a mixture of 80 parts by weight of alkylated benzene, 10parts by weight of the addition product of from 8 to 10 mol of ethyleneoxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight ofcalcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of theaddition product of 40 mol of ethylene oxide to 1 mol of castor oil; adispersion is obtained by finely dispersing the formulation in water.

III. a solution of 20 parts by weight of a compound I according to theinvention in a mixture of 40 parts by weight of cyclohexanone, 30 partsby weight of isobutanol, 20 parts by weight of the addition product of 7mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weightof the addition product of 40 mol of ethylene oxide to 1 mol of castoroil; a dispersion is obtained by finely dispersing the formulation inwater.

IV. an aqueous dispersion of 20 parts by weight of a compound Iaccording to the invention in a mixture of 25 parts by weight ofcyclohexanone, 65 parts by weight of a petroleum fraction of boilingpoint from 210° to 280° C. and 10 parts by weight of the additionproduct of 40 mol of ethylene oxide to 1 mol of castor oil; a dispersionis obtained by finely dispersing the formulation in water.

V. a mixture, ground in a hamer mill, of 20 parts by weight of acompound I according to the invention, 3 parts by weight of the sodiumsalt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of thesodium salt of a lignosulfonic acid from a sulfite waste liquor and 60parts by weight of powdered silica gel; a spray mixture is obtained byfinely dispersing the mixture in water;

VI. an intimate mixture of 3 parts by weight of a compound I accordingto the invention and 97 parts by weight of finely divided kaolin; thisdusting composition contains 3% by weight of active compound;

VII. an intimate mixture of 30 parts by weight of a compound I accordingto the invention, 92 parts by weight of powdered silica gel and 8 partsby weight of liquid paraffin which has been sprayed onto the surface ofthis silica gel; this preparation gives the active compound a goodadhesion;

VIII. a stable aqueous dispersion of 40 parts by weight of a compound Iaccording to the invention, 10 parts by weight of the sodium salt of aphenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight ofsilica gel and 48 parts by weight of water, which can be furtherdiluted;

IX. a stable oily dispersion of 20 parts by weight of a compound Iaccording to the invention, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, 8 parts by weight of fatty alcoholpolyglycol ether, 2 parts by weight of the sodium salt of aphenolsulfonic acid/urea/formaldehyde condensate and 68 parts by weightof a paraffinic mineral oil;

X. a mixture, ground in a hammer mill, of 10 parts by weight of acompound I according to the invention, 4 parts by weight of the sodiumsalt of diisobutylnaphthalene-α-sulfonic acid, 20 parts by weight of thesodium salt of a lignosulfonic acid from a sulfite waste liquor,38-parts by weight of silica gel and 38 parts by weight of kaolin. Byfinely dispersing the mixture in 10,000 parts by weight of water, aspray mixture is obtained which contains 0.1% by weight of the activecompound.

The compounds I are applied by treating the fungi or the seeds, plants,materials or the soil to be protected from fungal attack with afungicidally active amount of the active compounds.

They are applied before or after the infection of the materials, plantsor seeds by the fungi.

Depending on the type of effect desired, the application rates are from0.02 to 3 kg of active compound per ha, preferably from 0.1 to 1 kg/ha.

In seed treatment, amounts of active compound of from 0.001 to 50 g,preferably from 0.01 to 10 g, per kilogram of seed are in generalneeded.

The application rate of active compound for controlling pests underoutdoor conditions is from 0.02 to 10, preferably from 0.1 to 2.0 kg/ha.

The compounds I, on their own or in combination with herbicides orfungicides, can also be applied jointly mixed with further cropprotection agents, for example with growth regulators or with agents forcontrolling pests or bacteria. Of interest is also the miscibility withfertilizers or with mineral salt solutions which are employed foreliminating nutritional and trace element deficiencies.

The crop protection agents and fertilizers can be added to thecompositions according to the invention in a weight ratio of from 1:10to 10:1, if appropriate even immediately before use (tank mix). Onmixing with fungicides or insecticides, in many cases an increase in thefungicidal spectrum of action is obtained here.

The following list of fungicides with which the compounds according tothe invention can be applied together is intended to illustrate thecombination possibilities, but not restrict them:

sulfur, dithiocarbamates and their derivatives, such as ferricdimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediamine bisdithiocarbamate, tetramethylthiuramdisulfides sic!, ammonia complex of zincN,N-ethylene-bisdithiocarbamate, ammonia complex of zincN,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithiocarbamate,N,N'-poly-propylenebis(thiocarbamoyl) disulfide; nitro derivatives, suchas dinitro-(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate, diisopropyl5-nitroisophthalate;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate, 5-amino-1-β-bis-(dimethylamino)-phosphinyl!-3-phenyl-1,2,4-triazole,2,3--dicyano-1,4--dithioanthraquinone, 2-thio-1,3-dithiolo-β-4,5-b!quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)benzimidazole,2-(thiazol-4-yl)-benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide,N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,pyridine-2-thio-1-oxide sic!, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methyl-furan-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis(1-(2,2,2-trichloroethyl))formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-3-(p-tert-butylphenyl)-2-methylpropyl!-cis-2,6-dimethylmorpholine, N-3-(p-tertbutylphenyl)-2-methylpropyl!piperidine, 1-2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl!-1H-1,2,4-triazole,1-2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl!-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolylurea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,

and also various fungicides, such as dodecylguanidine acetate, 3-3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl!glutarimide,hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-2-furoylalaninate, DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alanine methylester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-3,5-dichlorophenyl(-5-methyl-5-methoxymethyl!-1,3-oxazolidine-2,4-dionesic!, 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide,2-cyano- N ethylaminocarbonyl-2-methoximino!-acetamide, 1-2-(2,4-dichlorophenyl)pentyl!-1H-1,2,4-triazole,2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

SYNTHESIS EXAMPLES

The procedures described in the synthesis examples below were used withappropriate modification of the starting compounds to obtain furthercompounds I. The compounds thus obtained are listed with physical datain the following table.

Example 1 Methyl α-{2-1-(4-chlorophenyl)pyrazol-3-yloxy-methyl!phenyl}but-2-enoate 1.a Methylα-(2-bromomethylphenyl)but-2-enoate

Hydrogen bromide was passed at -5° C. into a solution of 14.8 g ofmethyl α- 2-(2-methylphenyloxymethyl)phenyl!but-2-enoate in 250 ml ofmethylene chloride until it was saturated (about 18 g of HBr). Aftertermination of the reaction (about 2 h at 25° C.), the solvent wasdistilled off under reduced pressure. The residue thus obtained wastaken up in 300 ml of cyclohexane. The solution was washed with 5%strength sodium hydroxide solution and then with water. After drying andconcentrating the organic phase, 8 g of the title compound were obtained(m.p.: 64°-66° C.).

1.b 1-(4-Chlorophenyl)-3-hydroxypyrazole

A solution of 57.5 g of 4-chlorophenylhydrazine hydrosulfate in 1,000 mlof tert-butanol was first treated in portions with 100.8 g of potassiumtert-butoxide and then (after stirring for 10 min) in the course of 45min at 45° C.-50° C. with a solution of 27.7 g of methyl propiolate in90 ml of tertbutanol. After 1 h at boiling point, the mixture wasallowed to cool and the solvent was removed under reduced pressure. Theresidue thus obtained was dissolved in 1,200 ml of water. The aqueousphase was first washed with methylene chloride and then acidified, theproduct being deposited as a solid. 47.6 g of the title compound wereobtained, m.p.: 185°-187° C.

1.c A mixture of 2.43 g of the product from 1.b, 2.58 g of potassiumcarbonate, 3.36 g of the product from 1.a and 33 ml of dimethylformamidewas stirred at 60° C. for 4 h. After cooling, the reaction mixture wastaken up in 300 ml of water. The product was isolated from the organicphase after extraction of the aqueous solution with methyl tert-butylether and then purified by chromatography. (Silica gel, cyclohexane/MTBE3:1). (4.5 g of the title compound, m.p.: 65°-66° C.).

Example 2 Methyl α-{2-1-phenyl-4,5-dihydropyrazol-3-yloxy-methyl!phenyl}but-2-enoate

A mixture of 2.43 g of N-phenylpyrazolidin-3-one, 3.1 g of potassiumcarbonate, 4.04 g of the product from 1.a and 40 ml of dimethylformamidewas stirred at 60° C. for 4 h. After cooling, the reaction mixture wastaken up in 300 ml of sodium chloride solution (dilute). The product wasisolated from the organic phase after extraction of the aqueous solutionwith methyl tert-butyl ether and then purified by chromatography onsilica gel using cyclohexane/methyl tert-butyl ether 5:1 (1.4 g of thetitle compound, m.p.: 90°-92° C.).

                                      TABLE                                       __________________________________________________________________________     ##STR8##                                                                     No.                                                                              Formula                                                                           R.sup.1.sub.n                                                                    R.sup.2                                                                             R.sup.3   m.p.  °C.!/IR cm.sup.-1 !/.sup.1                                       H-NMR ppm!                                          __________________________________________________________________________    1  I.1 H  H     Phenyl    68-69                                               2  I.1 H  H     4-Methylphenyl                                                                          65-66                                               3  I.1 H  H     3-Chlorophenyl                                                                          58-59                                               4  I.1 H  H     4-Chlorophenyl                                                                          65-66                                               5  I.1 H  H     4-Fluorophenyl                                                                          53-54                                               6  I.1 H  H     2,4-(Cl).sub.2 -phenyl                                                                  72-74                                               7  I.1 H  H     2,4-(CH.sub.3).sub.2 -phenyl                                                            1716, 1541, 1483,                                                             1463, 1434, 1358,                                                             1253, 1206, 1036, 747                               8  I.1 H  H     2-CH.sub.3 -4-Cl-phenyl                                                                 1715, 1543, 1495,                                                             1480, 1465, 1357,                                                             1254, 1036, 940, 748                                9  I.1 H  H     2-Cl-phenyl                                                                             1715, 1546, 1495,                                                             1477, 1451, 1358,                                                             1254, 1036, 758                                     10 I.1 H  H     3,5-(Cl).sub.2 -phenyl                                                                  90-92                                               11 I.1 H  H     2,6-(Cl).sub.2 -phenyl                                                                  1714, 1547, 1494,                                                             1469, 1439, 1356,                                                             1254, 1037, 793, 749                                12 I.1 H  H     2-CH.sub.3 -phenyl                                                                      1715, 1541, 1482,                                                             1463, 1435, 1358,                                                             1254, 1048, 1036                                    13 I.1 H  H     3-CH.sub.3 -phenyl                                                                      1715, 1545, 1495,                                                             1483, 1465, 1356,                                                             1253, 1052, 1036                                    14 I.1 H  H     4-OCH.sub.3 -phenyl                                                                     1714, 1543, 1517,                                                             1484, 1465, 1442,                                                             1359, 1251, 1049, 1035                              15 I.1 H  H     2,5-(Cl).sub.2 -phenyl                                                                  1715, 1548, 1490,                                                             1472, 1434, 1346,                                                             1254, 1056, 1029, 747                               16 I.1 H  H     3,4-(Cl).sub.2 -phenyl                                                                  97-98                                               17 I.1 H  H     3-CF.sub.3 -phenyl                                                                      78-79                                               18 I.1 H  H     5-CF.sub.3 -pyridin-2-yl                                                                54-56                                               19 I.1 H  4-Cl  4-CH.sub.3 -phenyl                                                                      67-68                                               20 I.1 H  4-Cl  4-Cl-phenyl                                                                             1713, 1555, 1512,                                                             1496, 1435, 1357,                                                             1255, 1123, 936, 828                                21 I.1 H  H     3-OCH.sub.3 -phenyl                                                                     1714, 1607, 1597,                                                             1545, 1476, 1356,                                                             1252, 1220, 1046, 1037                              22 I.1 H  H     3,4- OCF.sub.2O!                                                                        69-71                                                               phenyl                                                        23 I.1 H  4-COOCH.sub.3                                                                       4-Cl-phenyl                                                                             118-119                                             24 I.1 H  4-COOCH.sub.3                                                                       2,4-(Cl).sub.2 -phenyl                                                                  1715, 1564, 1511,                                                             1494, 1436, 1298,                                                             1284, 1254, 1209, 1112                              25 I.1 H  H     4-CF.sub.3 -phenyl                                                                      1714, 1617, 1551,                                                             1435, 1329, 1323,                                                             1255, 1121, 1112                                    26 I.1 H  H     Pyridin-2-yl                                                                            1715, 1594, 1547,                                                             1485, 1471, 1451,                                                             1355, 1254, 1047, 776                               27 I.1 H  5-CH.sub.3                                                                          Phenyl    73-74                                               28 I.1 H  5-CF.sub.3                                                                          2,4-(Cl).sub.2 -phenyl                                                                  1,61 (d,3H);                                                                  3,69 (s,3H);                                                                  5,08 (s,2H);                                                                  6,19 (s,1H);                                                                  7,08-7,60 (8H)                                      29 I.1 H  4-NO.sub.2                                                                          2,4-(Cl).sub.2 -phenyl                                                                  116-118                                             30 I.1 H  4-Cl  2,4-(Cl).sub.2 -phenyl                                                                  112-114                                             31 I.1 H  4-COOCH.sub.3                                                                       Phenyl    117-118                                             32 I.1 H  4-Cl  5-CF.sub.3 -pyridin-2-yl                                                                107-109                                             33 I.2 H  H     Phenyl    90-92                                               34 I.1 3-Cl                                                                             H     2,4-Cl.sub.2C.sub.6 H.sub.3                                                             1717, 1546, 1477, 1354, 1261,                                                 1218, 1055                                          35 I.1 3-Cl                                                                             H     3,5-Cl.sub.2C.sub.6 H.sub.3                                                             1715, 1591, 1578, 1549, 1458,                                                 1436, 1352, 1258                                    36 I.1 3-Cl                                                                             H     4-OCH.sub.3C.sub.6 H.sub.4                                                              1716, 1542, 1517, 1486, 1357,                                                 1252, 1045, 1029                                    37 I.1 3-Cl                                                                             H     5-CF.sub.3 -pyridin-2-yl                                                                116-118                                             38 I.2 H  H     4-ClC.sub.6 H.sub.4                                                                     1715, 1639, 1598, 1495, 1434,                                                 1415, 1354, 1255                                    39 I.2 H  H     2,4-Cl.sub.2C.sub.6 H.sub.3                                                             115-116                                             40 I.1 H  H     CH.sub.2 C.sub.6 H.sub.5                                                                1714, 1537, 1490, 1455, 1434,                                                 1362, 1254, 1049, 1036                              41 I.1 H  H     CH.sub.2(4-ClC.sub.6 H.sub.4)                                                           1714, 1537, 1492, 1434, 1362,                                                 1254, 1049, 1036, 1016                              42 I.1 H  5-CO.sub.2 CH.sub.3                                                                 CH.sub.2 C.sub.6 H.sub.5                                                                1720, 1543, 1481, 1455, 1435,                                                 1261, 1207, 1089, 1037                              43 I.1 H  H     5-Cl-pyridin-2-yl                                                                       76-78                                               44 I.1 H  H     6-Cl-pyridazin-3-yl                                                                     106-108                                             45 I.1 H  H     pyrazin-2-yl                                                                            89-91                                               46 I.1 H  4-Cl  C.sub.6 H.sub.5                                                                         1713, 1599, 1555, 1512, 1500,                                                 1357, 1254, 1121                                    47 I.1 H  4-Cl  pyrazin-2-yl                                                                            97-99                                               48 I.1 H  4-Br  4-ClC.sub.6 H.sub.4                                                                     88-90                                               49 I.1 H  4-NO.sub.2                                                                          5-CF.sub.3 -pyridin-2-yl                                                                112-114                                             50 I.1 H  H     CH.sub.2(2,4-Cl.sub.2C.sub.6 H.sub.3)                                                   61-64                                               51 I.1 H  H     2-Cl, 4-FC.sub.6 H.sub.3                                                                1715, 1547, 1505, 1481, 1465,                                                 1358, 1257, 1205, 1051, 1038                        52 I.1 H  H     2-CH.sub.3, 4-FC.sub.6 H.sub.3                                                          55-57                                               53 I.2 H  H     2-Cl, 4-FC.sub.6 H.sub.3                                                                82-84                                               54 I.1 H  H     6-Cl-pyridin-2-yl                                                                       111-113                                             __________________________________________________________________________

Examples of the Action Against Harmful Fungi

It was possible to show the fungicidal action of the compounds of theformula I by the following experiments:

The active compounds were prepared as a 20% strength emulsion in amixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN(Lutensol® AP6, wetting agent having emulsifying and dispersant actionbased on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL(Emulan® EL, emulsifier based on ethoxylated fatty alcohols) andaccordingly diluted to the desired concentration with water.

The comparison compounds used were the following active compoundsdisclosed in EP-A 513 580:

A Example No. 17 from EP-A 513 580

B Example No. 56 from EP-A 513 580

C Example No. 57 from EP-A 513 580

D Example No. 143 from EP-A 513 580

E Example No. 144 from EP-A 513 580

F Example No. 145 from EP-A 513 580

1. Erysiphe graminis var. tritici

Leaves of wheat seedlings (Fruhgold variety) were first treated with theaqueous preparation of the active compounds (16 ppm-containingpreparation). After about 24 h, the plants were dusted with spores ofwheat mildew (Erysiphe graminis var. tritici). The plants treated inthis way were then incubated for 7 days at 20°-22° C. and a relativeatmospheric humidity of 75-80%. The extent of the fungal development wasthen determined. Assessment was carried out visually.

In this test, the plants treated with compounds 1, 2, 3, 4, 5, 6, 10 12,13, 15, 16 and 17 according to the invention showed an attack of 15% orless, while the plants treated with the known active compounds wereattacked to 70% (A and C), 60% (B) or 30% (D, E and F). The attack inthe case of the untreated control plants was 70%.

2. Plasmopara viticola

Potted vines (variety: Muller Thurgau) were sprayed with the activecompound preparation until dripping wet. After 8 days, the plants weresprayed with a zoospore suspension of the fungus Plasmopara viticola andkept for 5 days at 20°-30° C. at high atmospheric humidity. Beforeassessment, the plants were then kept for 16 h at high atmospherichumidity.

Assessment was carried out visually.

In this test, the plants treated with 63 ppm-containing preparations ofthe compounds 1, 2, 4, 5, 6, 7, 8, 9, 12, 13, 14 and 18 according to theinvention showed an attack of 5% or less, while the plants treated with125 ppm-containing preparations of the known active compounds wereattacked to 60% (A and F), 40%, (C) or 25% (E). The attack on theuntreated control plants was 60%.

We claim:
 1. A methyl α-phenylbutenoate of the formula I ##STR9## where-- is a single or double bond and the index and the substituents havethe following meanings:n is 0, 1, 2, 3 or 4, it being possible for thesubstituents R¹ to be different if n is greater than 1; R¹ is nitro,cyano, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl or C₁ -C₄ -alkoxy; R²is hydrogen, nitro, cyano, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₄ -alkoxycarbonyl; R³ isunsubstituted or substituted alkyl, alkenyl or alkynyl; an unsubstitutedor substituted saturated or mono-or diunsaturated ring which, inaddition to carbon atoms, optionally contains one to three of thefollowing heteroatoms as ring members: oxygen, sulfur and nitrogen, oran unsubstituted or substituted mono-or binuclear aromatic radicalwhich, in addition to carbon atoms optionally contains one to fournitrogen atoms or one or two nitrogen atoms and an oxygen or sulfur atomor an oxygen or sulfur atom as ring members.
 2. A process for preparingthe compounds of the formula I as claimed in claim 1, which comprisesreacting a benzyl derivative of the formula II ##STR10## where L is anucleophilically replaceable group, in the presence of a base with a3-hydroxy(dihydro)pyrazole of the formula III ##STR11##
 3. A mixturesuitable for controlling harmful fungi, containing an inert additive andan active amount of a compound of the formula I as claimed in claim 1.4. A mixture suitable for controlling animal pests, containing an inertadditive and an active amount of a compound of the formula I as claimedin claim
 1. 5. A method of controlling harmful fungi, which comprisestreating the harmful fungi, their habitat or the plants, surfaces,materials or spaces to be kept free from them with an active amount of acompound of the formula I as claimed in claim
 1. 6. A method ofcontrolling animal pests, which comprises treating the pests, theirhabitat or the plants, surfaces, materials or spaces to be kept freefrom them with an active amount of a compound of the formula I asclaimed in claim 1.